Mono-ketones of the pyrene series and process of making the same



Patented Feb. 2, 1937 UNITED STATES MONO-KETONES OF THE PYRENE SERIES AND PROCESS OF MAKING THE SAME Roland Scholl, Dresden, Kurt Meyer, Berlin- Zehlendorf, and Joachim Donat, Dresden,

Germany No Drawing.

Application January 24, 1936,

Serial No. 60,700. In Switzerland February 2,

19 Claims.

It is known that ketones of highly condensed ring systems may be obtained by causing an aroylchloride to react with a pyrene in presence of a condensing agent, but hitherto this reaction 5' could only be carried out in such a manner that there was obtained a mixture of monoand polyketones which had to be purified in a circumstantial manner.

This invention relates to a process which allows to produce mono-ketones from pyrene and halides of aromatic carboxylic acids in a uniform manner. The new process consists in causing pyrene to react at temperatures not exceeding 50 C. and in presence of a metal halide selected from the group consisting of aluminium chloride and ferric chloride and of such a solvent selected from the group of solvents which are suitable for the Friedel-Crafts reaction, which solvent is free of nitrogen and contains at least two carbon atoms united to each other, with one molecular proportion of a halide of an aromatic carboxylic acid selected from the group comprising the aromatic carboxylic acids of the benzene and naphthalene series, which group is characterized by the presence of the atom grouping is within the aromatic nucleus, as is the case with 40 the benzoic acid of the formula or wherein it is outside the aromatic neucleus, as is the case with the cinnamic acid of the 50 formula Such acids are, for example, benzoic acid, halogenated benzoic acid, toluic acids, 00- and ,3- naphthoic acids or cinnamic acids and the like.

60 The halides coming into question are above all the chlorides, there may however also be used other halides, such as, for example, bromides.

As solvents which are suitable for the new process there comes into question among the solvents which, as is known, are suitable for the Friedel-Crafts reaction, only those solvents which contain at least two carbon atoms united to each other and are free of nitrogen, and among these solvents particularly those selected from the group consisting of tetrachlo-rethane, benzene, chlorobenzene and toluene. The ketones obtainable according to the present process correspond to the general formula in which R represents an aromatic nucleus of the benzene or naphthalene series which may be linked to the (JO-group by a group. Among these ketones those are particularly valuable in which the radical R consists of more than six carbon atoms, such as the ketones deriving from toluic acids, naphthoic acids and cinnamic acids. They are yellow powders having a characteristic melting point, and are soluble in concentrated sulfuric acid with formation of coloured solutions which are at first more or less reddish or bluish-violet. The new ketones may be halogenated and are valuable intermediate products for making further intermediate products and vat-dyestuffs.

The following example illustrates the invention:-

10 parts by weight of pyrene in 100 parts by volume of benzene are shaken with 9.1 parts by weight of benzoyl chloride and 7 parts by weight of aluminium chloride for hours at 20 C. After removing the solvent by means of steam there is obtained a residual resinous product which may be recrystallized from glacial acetic acid. This substance constitutes 12 parts by weight or 80 per cent. of the theoretical yield of a pure monobenzoyl-pyrene. Also only a mono-benzoyl-pyrene is obtained when the benzoyl chloride is used in large excess. The same result is obtained when using benzoylbromide or when substituting for the aluminium chloride iron chloride or for the benzene toluene, chlorobenzene, tetrachlorethane, dichlorobenzene or a mixture of dichlorobenzenes which is liquid at ordinary temperature.

which, however, must not exceed 50 C. ,7

By substituting for the bnezoyl chloride parabromo-benzoyl-chloride, ,B-naphthoic acid-chloride, para-toluic acid-chloride or cinnamic acidchloride there are obtained respectively the parabromobenzoyl-pyrene of melting point I'M-175 C., the c-naphthoyl-pyrene of melting point 151" C., the para-toluyl-pyrene of melting point 155-156 C., and the mono-cinnamyl-pyrene of melting point 120-l2l C. and from the orthochlorobenzoyl-chloride the ortho-chlorobenzoylpyrene of melting point 151.5-l52.5 C. These products are yellow crystalline powders which dissolve in cold sulfuric acid to red-violet solutions. What we claim is: r

1. Process for the manufacture of monoketones of the pyrene series, consisting in causing a pyrene to react at temperatures not exceeding 50 C. and in presence of a metal halide selected from the group consisting of aluminium chloride and ferric chloride and of such a solvent selected from the group of solvents which are suitable for the Friedel-Crafts reaction, which solvent is free of nitrogen and contains at least two carbon atoms, united to each other, with one 7 molecular proportion of an aromatic carboxylic acid halide selected fromthegroup consisting of the aromatic mono-carboxylic acids of the benzene and naphthalene series, which group is characterized V by the presence of the atom grouping H H o 2. Process for the manufacture of monoketones of the pyrene series, consisting in causing a pyrene to react at temperatures not exceeding 50 C. and in presence of a metal halide selected from the group consisting of aluminium chloride and ferricchloride and of such a solvent selected from the group of solvents which are suitable for the Friedel-Crafts reaction, which solvent is free of nitrogen and contains at least two carbon atoms united to each other, with one molecular proportion of a chloride of an aromatic carboxylic acid selected from the group consisting of the aromatic mono-carboxylic acids of the benzene and naphthalene series, which group is'characterized by the presence of the atom grouping H 0 new 3. Process for the manufacture of monoketones of the pyrene series, consisting in caus ing a pyrene to react at temperatures not exceeding 30 C. and in presence of a metal halide selected from the group consisting of aluminium chloride and ferric chloride and of a solvent selected from the group of solvents consisting of V tetrachlorethane, benzene, chlorobenzene and toluene, with one molecular proportion of a chloride of an aromatic carboxylic acid selected from the group consisting of the aromatic monocarboxylic acids of the benzene and naphthalene The operation may also be carried out at a somewhat raised temperature series, which group is characterized by the presence of the atom grouping 4. Process for the manufacture of monoketones of the pyrene series, consisting in causing a pyrene to react at temperatures not exceeding 30 C. and in presence of ametal halide selected from the group consisting of aluminium chloride and ferric chloride and of benzene, with 5. Process for the manufacture of monoketonesof the pyrene series, consisting in causing a pyrene to react'at temperatures not exceeding 50 C. and in presence of a metal halide selected from the group consisting of aluminium chloride and ferric chloride and of such a solvent selected from the group of solvents which are suitable for the Friedel-Crafts reaction, which solvent is free of nitrogen and contains at least two carbon atoms united to'each other, with one molecular proportion of a chloride of an aromatic carboxylic acid containing at least 8 carbon atoms and selected from the group consisting of the aromatic mono-carboxylic acids of the benzene and naphthalene series, which group is characterized by the presence of the atom grouping 6. Process for the manufacture of monoketones of the pyrene series, consisting in caus ing a pyrene to react at temperatures not exceeding 50 C. and in presence of aluminium chloride and of such a solvent selected from the group of solvents which are suitable for the Friedel-Crafts reaction, which solvent is free of nitrogen and contains at least two carbon atoms united to each'other, with one molecular proportion of a chloride of an aromatic carboxylic acid containing at least 8 carbon atomsselected' from the group consisting of the aromatic monocarboxylic acids of the benzene and naphthalene series, which group is characterized by the presence of the atom grouping '7. Process for the manufacture of monoketones of the pyrene series, consisting in causing a pyrene to react at temperatures not exceeding 30 C. and in presence of aluminium chloride and of a solvent selected from the group of solvents consisting of tetrachloroethane, benand naphthalene series, which group is characterized by the presence of the atom grouping H H I I I -0=co 8. Process for the manufacture of monoketones of the pyrene series, consisting in causing a pyrene to react at temperatures not exceeding 30 C. and in presence of aluminium chloride and of benzene, with one molecular pro portion of a chloride of an aromatic carboxylic acid containing at least 8 carbon atoms selected from the group consisting of the aromatic monocarboxylic acids of the benzene and naphthalene series, which group is characterized by the presence of the atom grouping 9. Process for the manufacture of monoketones of the pyrene series, consisting in cansing a pyrene to react at temperatures not exceeding 50 C. and in presence of aluminium chloride and of such a solvent selected from the group of solvents which are suitable for the Friedel-Crafts reaction, which solvent is free of nitrogen and contains at least two carbon atoms united to each other, with one molecular proportion of a chloride of an aromatic carboxylic acid containing at least 8 carbon atoms selected from the group consisting of the aromatic monocarboxylic acids of the benzene series, which group is characterized by the presence of the atom grouping 10. Process for the manufacture of monoketones of the pyrene series, consisting in causing a pyrene to react at temperatures not exceeding 50 C. and in presence of aluminium chloride and of such a solvent selected from the group of solvents which are suitable for the Friedel-Crafts reaction, which solvent is free of nitrogen and contains at least two carbon atoms united to each other, with one molecular proportion of the chloride of a toluic acid.

11. Process for the manufacture of monoketones of the pyrene series, consisting in causing a pyrene to react at temperatures not exceeding 30 C. and in presence of aluminium chloride and of a solvent selected from the group of solvents consisting of tetrachlorethane, benzene, chlorobenzene and toluene, with one molecular proportion of the chloride of a toluic acid.

12. Process for the manufacture of monoketones of the pyrene series, consisting in causing a pyrene to react at temperatures not exceeding 30 C. and in presence of aluminium chloride and of benzene, with one molecular proportion of the chloride of a toluic acid.

13. Process for the manufacture of monoketones of the pyrene series, consisting in causing a pyrene to react at temperatures not exceeding 50 C. and in presence of aluminium chloride and of such a solvent selected from the group of solvents which are suitable for the Friedel- Crafts reaction, which solvent is free of nitrogen and contains at least two carbon atoms united to each other, with one molecular proportion of a chloride of the cinnamic acid.

14. Process for the manufacture of monoketones of the pyrene series, consisting in causing a pyrene to react at temperatures not exceeding 30 C. and in presence of aluminium chloride and of a solvent selected from the group of solvents consisting of tetrachloroethane, benzene, chlorobenzene and toluene, with one molecular proportion of a chloride of the cinnamic acid.

15. Process for the manufacture of monoketones of the pyrene series, consisting in causing a pyrene to react at temperatures not exceeding 30 C. and in presence of aluminium chloride and of benzene, with one molecular proportion of a chloride of the cinnamic acid.

16. Process for the manufacture of monoketones of the pyrene series, consisting in causing a pyrene to react at temperatures not exceeding 50 C. and in presence of aluminium chloride and of such a solvent selected from the group of solvents which are suitable for the Friedel-Crafts reaction, which solvent is free of nitrogen and contains at least two carbon atoms united to each other, with one molecular proportion of a chloride of a naphthoic acid.

1'7. Process for the manufacture of monoketones of the pyrene series, consisting in causing a pyrene to react at temperatures 'not exceeding 30 C. and in presence of aluminium chloride and of a solvent selected from the group of solvents consisting of tetrachloroethane, benzene, chlorobenzene and toluene, with one molecular proportion of a chloride of a naphthoic acid.

18. Process for the manufacture of monoketones of the pyrene series, consisting in causing a pyrene to react at temperatures not exceeding 30 C. and in presence of aluminium chloride and. of benzene, with one molecular proportion of a chloride of a naphthoic acid.

19. The mono-ketones of the pyrene series of the general formula in which R stands for an aromatic radical selected from the group consisting of tolyl, cinnamyl and naphthyl, which products are yellow powders soluble in sulfuric acid to red-violet solutions.

' ROLAND SCI-IOLL.

KURT MEYER. JOACHIM DONAT. 

